Vapor Jet Printing

ABSTRACT

Embodiments of the disclosed subject matter provide systems and methods of depositing a film on a selective area of a substrate. A first jet of a first material may be ejected from a first nozzle assembly of a jet head having a plurality of nozzle assemblies to form a first portion of a film deposition on the substrate. A second jet of a second material may be ejected from a second nozzle assembly of the plurality of nozzle assemblies, the second nozzle assembly being aligned with the first nozzle assembly parallel to a direction of motion between the plurality of nozzle assemblies and the substrate, and the second material being different than the first material. The second material may react with the first portion of the film deposition to form a composite film deposition on the substrate when using reactive gas precursors.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/292,422, filed on Mar. 5, 2019, which claims priority to U.S. PatentApplication Ser. No. 62/651,780, filed Apr. 3, 2018, the entire contentsof each are incorporated herein by reference.

FIELD

The present invention relates to compounds for use as emitters, anddevices, such as organic light emitting diodes, including the same.

BACKGROUND

Opto-electronic devices that make use of organic materials are becomingincreasingly desirable for a number of reasons. Many of the materialsused to make such devices are relatively inexpensive, so organicopto-electronic devices have the potential for cost advantages overinorganic devices. In addition, the inherent properties of organicmaterials, such as their flexibility, may make them well suited forparticular applications such as fabrication on a flexible substrate.Examples of organic opto-electronic devices include organic lightemitting diodes/devices (OLEDs), organic phototransistors, organicphotovoltaic cells, and organic photodetectors. For OLEDs, the organicmaterials may have performance advantages over conventional materials.For example, the wavelength at which an organic emissive layer emitslight may generally be readily tuned with appropriate dopants.

OLEDs make use of thin organic films that emit light when voltage isapplied across the device. OLEDs are becoming an increasinglyinteresting technology for use in applications such as flat paneldisplays, illumination, and backlighting. Several OLED materials andconfigurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and5,707,745, which are incorporated herein by reference in their entirety.

One application for phosphorescent emissive molecules is a full colordisplay. Industry standards for such a display call for pixels adaptedto emit particular colors, referred to as “saturated” colors. Inparticular, these standards call for saturated red, green, and bluepixels. Alternatively the OLED can be designed to emit white light. Inconventional liquid crystal displays emission from a white backlight isfiltered using absorption filters to produce red, green and blueemission. The same technique can also be used with OLEDs. The white OLEDcan be either a single EML device or a stack structure. Color may bemeasured using CIE coordinates, which are well known to the art.

As used herein, the term “organic” includes polymeric materials as wellas small molecule organic materials that may be used to fabricateorganic opto-electronic devices. “Small molecule” refers to any organicmaterial that is not a polymer, and “small molecules” may actually bequite large. Small molecules may include repeat units in somecircumstances. For example, using a long chain alkyl group as asubstituent does not remove a molecule from the “small molecule” class.Small molecules may also be incorporated into polymers, for example as apendent group on a polymer backbone or as a part of the backbone. Smallmolecules may also serve as the core moiety of a dendrimer, whichconsists of a series of chemical shells built on the core moiety. Thecore moiety of a dendrimer may be a fluorescent or phosphorescent smallmolecule emitter. A dendrimer may be a “small molecule,” and it isbelieved that all dendrimers currently used in the field of OLEDs aresmall molecules.

As used herein, “top” means furthest away from the substrate, while“bottom” means closest to the substrate. Where a first layer isdescribed as “disposed over” a second layer, the first layer is disposedfurther away from substrate. There may be other layers between the firstand second layer, unless it is specified that the first layer is “incontact with” the second layer. For example, a cathode may be describedas “disposed over” an anode, even though there are various organiclayers in between.

As used herein, “solution processable” means capable of being dissolved,dispersed, or transported in and/or deposited from a liquid medium,either in solution or suspension form.

A ligand may be referred to as “photoactive” when it is believed thatthe ligand directly contributes to the photoactive properties of anemissive material. A ligand may be referred to as “ancillary” when it isbelieved that the ligand does not contribute to the photoactiveproperties of an emissive material, although an ancillary ligand mayalter the properties of a photoactive ligand.

As used herein, and as would be generally understood by one skilled inthe art, a first “Highest Occupied Molecular Orbital” (HOMO) or “LowestUnoccupied Molecular Orbital” (LUMO) energy level is “greater than” or“higher than” a second HOMO or LUMO energy level if the first energylevel is closer to the vacuum energy level. Since ionization potentials(IP) are measured as a negative energy relative to a vacuum level, ahigher HOMO energy level corresponds to an IP having a smaller absolutevalue (an IP that is less negative). Similarly, a higher LUMO energylevel corresponds to an electron affinity (EA) having a smaller absolutevalue (an EA that is less negative). On a conventional energy leveldiagram, with the vacuum level at the top, the LUMO energy level of amaterial is higher than the HOMO energy level of the same material. A“higher” HOMO or LUMO energy level appears closer to the top of such adiagram than a “lower” HOMO or LUMO energy level.

As used herein, and as would be generally understood by one skilled inthe art, a first work function is “greater than” or “higher than” asecond work function if the first work function has a higher absolutevalue. Because work functions are generally measured as negative numbersrelative to vacuum level, this means that a “higher” work function ismore negative. On a conventional energy level diagram, with the vacuumlevel at the top, a “higher” work function is illustrated as furtheraway from the vacuum level in the downward direction. Thus, thedefinitions of HOMO and LUMO energy levels follow a different conventionthan work functions.

More details on OLEDs, and the definitions described above, can be foundin U.S. Pat. No. 7,279,704, which is incorporated herein by reference inits entirety.

SUMMARY

According to an embodiment, an organic light emitting diode/device(OLED) is also provided. The OLED can include an anode, a cathode, andan organic layer, disposed between the anode and the cathode. Accordingto an embodiment, the organic light emitting device is incorporated intoone or more device selected from a consumer product, an electroniccomponent module, and/or a lighting panel.

According to an embodiment, a method of depositing a film on a selectivearea of a substrate may be provided. A first jet of a first material maybe ejected from a first nozzle assembly of a jet head comprising aplurality of nozzle assemblies to form a first portion of a filmdeposition on the substrate. A second jet of a second material may beejected from a second nozzle assembly of the plurality of nozzleassemblies, the second nozzle assembly being aligned with the firstnozzle assembly parallel to a direction of motion between the pluralityof nozzle assemblies and the substrate, and the second material beingdifferent than the first material. The second material may react withthe first portion of the film deposition to form a composite filmdeposition on the substrate when using reactive gas precursors.

Each nozzle of the plurality of nozzle assemblies may include jettingapertures, exhaust apertures, and confinement apertures, and a jettingflow ejected from the jetting apertures may be perpendicular to thesubstrate, and a confinement flow ejected from the confinement aperturesmay be parallel to the substrate. A shape and a thickness profile of thecomposite film deposition, and the selective area of the substrate uponwhich the composite film deposition is formed, may be based on a sizeand shape of the first nozzle assembly and the second nozzle assembly,and a distance between the jet head and the substrate.

The selective area of the substrate upon which the composite filmdeposition is formed may be less than 50% of the surface area of thesubstrate, and may be less than 10% of the surface area of thesubstrate. A size of the jet head may be less than 10% of a surface areaof the substrate. At least one of a length and width dimension of thejet head may be less than 25% of at least one of a length and widthdimension of the substrate. The distance between the substrate and thejet head may be 10-100 μm, but may extend up to 1 mm for low resolutionprinting applications.

The composite film deposition may include at least one of an inorganicfilm, a metal film, and an organic film. The composite film depositionmay be formed by using at least one of an atomic layer deposition (ALD),an atomic layer epitaxy (ALE), a chemical vapor deposition (CVD), plasmaenhanced chemical vapor deposition (PECVD), and remote plasma enhancedchemical vapor deposition (RPECVD). The composite film deposition mayform a multi-layer barrier film over at least a portion of an organiclight emitting device (OLED). The composite film deposition may includeat least one of Group III-V materials. The Group III-V materials may bedeposited using a showerhead having separate gas pathways for the GroupIII materials and the Group V materials. The composite film depositionmay be formed from at least one of GaAs, AlAs, InGaAs, InP, InGaAlP,GaN, AlGaN, GaInN, and AlN. The composite film deposition may be athree-dimensional structure of at least one material selected from anorganic material, an inorganic material, a metallic material, and adielectric material. The composite film deposition may be aspatially-localized thin film transistor, a light emitting device, or anorganic light emitting device.

The method may include detecting, with a sensor, one or more surfacefeatures of a device, where the composite film deposition is formed onthe one or more detected surface features of the device. One of thedetected surface features may be a surface defect.

An embodiment of the disclosed subject matter may provide a device todeposit a film on a selective area of a substrate. The device mayinclude a jet head having a plurality of nozzle assemblies. Theplurality of nozzle assemblies may include a first nozzle assembly toeject a first jet of a first material to form a first portion of a filmdeposition on the substrate, and a second nozzle assembly to eject asecond jet of a second material, the second nozzle assembly beingaligned with the first nozzle assembly parallel to a direction of motionbetween the plurality of nozzle assemblies and the substrate, and thesecond material being different than the first material. The secondmaterial may react with the first portion of the film deposition to forma composite film deposition on the substrate when using reactive gasprecursors.

Each nozzle of the plurality of nozzle assemblies may include of jettingapertures, exhaust apertures, and confinement apertures, and a jettingflow ejected from the jetting apertures is perpendicular to thesubstrate, and a confinement flow ejected from the confinement aperturesis parallel to the substrate. A deposition channel in each of theplurality of print head assemblies may be in fluid communication withthe jetting apertures. Exhaust channels, in fluid communication with theexhaust apertures, may be disposed adjacent to each deposition channel.Confinement channels, in fluid communication with the confinementapertures, may be disposed between the exhaust channels.

A shape and a thickness profile of the composite film deposition, andthe selective area of the substrate upon which the composite filmdeposition is formed, may be based on a size and shape of the firstnozzle assembly and the second nozzle assembly, and a distance betweenthe jet head and the substrate. The nozzle assemblies that eject thefirst material and the second material may be surrounded by a perimeterof inert convectors that do not emit reactive gasses.

According to an embodiment, a method of depositing films on a selectivearea of a substrate may rely on different source gases that react at orclose to a deposition site may be provided. A first jet of a firstmaterial may be ejected from a first nozzle assembly of a jet head thatis separate from a second nozzle assembly of the jet head. On a surfaceof the substrate, a first layer deposition may be formed using the firstmaterial. The substrate or the jet head may be moved a distancecorresponding to a spacing between the first nozzle assembly and thesecond nozzle assembly. A second jet of a second material may be ejectedfrom the second nozzle assembly of the jet head. The second nozzleassembly may be aligned with the first nozzle assembly parallel to adirection of motion between the plurality of nozzle assemblies and thesubstrate. The second material may react with the first portion of thefilm deposition to form a composite film deposition on the substratewhen using reactive gas precursors.

The first nozzle assembly and the second nozzle assembly may be confinedfrom one another. Each nozzle of a plurality of nozzle assemblies of thejet head may include jetting apertures, exhaust apertures, andconfinement apertures, and a jetting flow ejected from the jettingapertures may be perpendicular to the substrate, and a confinement flowejected from the confinement apertures may be parallel to the substrate.A shape and a thickness profile of the composite film deposition, andthe selective area of the substrate upon which the composite filmdeposition is formed, may be based on a size and shape of the firstnozzle assembly and the second nozzle assembly, and a distance betweenthe jet head and the substrate.

The substrate or the jet head may be moved the distance corresponding tothe spacing between the first nozzle assembly and the second nozzleassembly. The composite film deposition may be added to using the firstmaterial that is emitted from the first nozzle assembly.

The first nozzle assembly and the second nozzle assembly may form anozzle assembly pair, where a number of nozzle assembly pairs of theplurality of nozzle assemblies may be equal to a film thickness dividedby a bi-layer atom thickness.

The selective area of the substrate upon which the composite filmdeposition is formed may be less than 50% of the surface area of thesubstrate, and may be less than 10% of the surface area of thesubstrate. A size of the jet head may be less than 10% of a surface areaof the substrate. At least one of a length and width dimension of thejet head may be less than 25% of at least one of a length and widthdimension of the substrate. The distance between the substrate and thejet head may be 10-100 μm, but may extend up to 1 mm for low resolutionprinting applications.

The composite film deposition may include at least one of an inorganicfilm, a metal film, and an organic film. The composite film depositionmay be formed using at least one of an atomic layer deposition (ALD), anatomic layer epitaxy (ALE), a chemical vapor deposition (CVD), plasmaenhanced chemical vapor deposition (PECVD), and remote plasma enhancedchemical vapor deposition (RPECVD). The composite film deposition formsa multi-layer barrier film over at least a portion of an organic lightemitting device (OLED). The composite film deposition may be aspatially-localized thin film transistor, a light emitting device, or anorganic light emitting device.

The method may include detecting, with a sensor, one or more surfacefeatures of a device, where the composite film deposition is formed onthe one or more detected surface features of the device. One of thedetected surface features may be a surface defect.

According to an embodiment, a system may be provided to deposit a filmon a selective area of a substrate. A jet head having a plurality ofnozzle assemblies may include a first nozzle assembly to eject a firstjet of a first material to form, on a surface of the substrate, a firstlayer deposition using the first material, and a second nozzle assemblyto eject a second jet of a second material when the substrate or the jethead is moved a distance corresponding to a spacing between the firstnozzle assembly and the second nozzle assembly. The second nozzleassembly may be aligned with the first nozzle assembly parallel to adirection of motion between the plurality of nozzle assemblies and thesubstrate. The second material may react with the first portion of thefilm deposition to form a composite film deposition on the substratewhen using reactive gas precursors.

The first nozzle assembly of a jet head may be separate from a secondnozzle assembly of the jet head, where the first nozzle assembly and thesecond nozzle assembly are confined from one another, and where eachnozzle of a plurality of nozzle assemblies of the jet head is comprisedof jetting apertures, exhaust apertures, and confinement apertures, anda jetting flow ejected from the jetting apertures is perpendicular tothe substrate, and a confinement flow ejected from the confinementapertures is parallel to the substrate. A shape and a thickness profileof the composite film deposition, and the selective area of thesubstrate upon which the composite film deposition is formed, may bebased on a size and shape of the first nozzle assembly and the secondnozzle assembly, and a distance between the jet head and the substrate.The first nozzle assembly and the second nozzle assembly may form anozzle assembly pair, wherein a number of nozzle assembly pairs of theplurality of alternating nozzles is equal to a film thickness divided bya bi-layer atom thickness.

According to an embodiment, a method of depositing a film on a selectivearea of an object may be provided. The method may include switchingbetween a source for a first gas and a second gas. The first gas may beejected from a first nozzle assembly of a jet head having a plurality ofnozzle assemblies, and the second gas may be ejected from a secondnozzle assembly of the jet head, where the second nozzle assembly isaligned with the first nozzle assembly parallel to a direction of motionbetween the plurality of nozzle assemblies and the object. The methodmay include forming, on a surface of the object, a composite filmdeposition by alternating the exposure of the surface of the object tothe first gas and the second gas by the switching, where the compositefilm deposition is formed using reactive gas precursors.

Each nozzle of the plurality of nozzle assemblies is comprised ofjetting apertures, exhaust apertures, and confinement apertures, and ajetting flow ejected from the jetting apertures is perpendicular to theobject, and a confinement flow ejected from the confinement apertures isparallel to the object.

A shape and a thickness profile of the composite film deposition, andthe selective area of the object upon which the composite filmdeposition is formed, may be based on a size and shape of the firstnozzle assembly and the second nozzle assembly, and a distance betweenthe jet head and the object. The object may be a substrate or a device.

The selective area of the object upon which the composite filmdeposition is formed may be less than 50% of the surface area of theobject, and may be less than 10% of the surface area of the object. Asize of the jet head may be less than 10% of a surface area of theobject. At least one of a length and width dimension of the jet head maybe less than 25% of at least one of a length and width dimension of theobject. The distance between the object and the jet head may be 10-100μm, but may extend up to 1 mm for low resolution printing applications.The formed composite film deposition may include at least one of aninorganic film, a metal film, and an organic film.

The composite film deposition may be formed using at least one of anatomic layer deposition (ALD), an atomic layer epitaxy (ALE), a chemicalvapor deposition (CVD), plasma enhanced chemical vapor deposition(PECVD), and remote plasma enhanced chemical vapor deposition (RPECVD).The composite film deposition may form a multi-layer barrier film overat least a portion of the device that is an organic light emittingdevice (OLED).

According to an embodiment, a system to depositing a film on a selectivearea of an object may be provided. The system may include a first sourcefor a first gas, a second source for a second gas, and a switch toselect between the first source and the second source. The first gas maybe ejected from a first nozzle assembly of a jet head comprising aplurality of nozzle assemblies, and the second gas may be ejected from asecond nozzle assembly of the jet head. The second nozzle assembly maybe aligned with the first nozzle assembly parallel to a direction ofmotion between the plurality of nozzle assemblies and the object. Acomposite film deposition may be formed on a surface of the object byalternating the exposure of the surface of the object to the first gasand the second gas using the switch. The composite film deposition maybe formed using reactive gas precursors.

Each nozzle of the plurality of nozzle assemblies may include of jettingapertures, exhaust apertures, and confinement apertures, and a jettingflow ejected from the jetting apertures is perpendicular to the object,and a confinement flow ejected from the confinement apertures isparallel to the object. A shape and a thickness profile of the compositefilm deposition, and the selective area of the object upon which thecomposite film deposition is formed, may be based on a size and shape ofthe first nozzle assembly and the second nozzle assembly, and a distancebetween the jet head and the object.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an organic light emitting device.

FIG. 2 shows an inverted organic light emitting device that does nothave a separate electron transport layer.

FIGS. 3A-3B show an OVJP (Organic Vapor Jet Printing) depositor, and amicronozzle array on which one or more OVJP depositors are arranged.

FIG. 4 shows a section of a micronozzle array having a plurality oftime-stable DEC (Depositor-Exhaust-Confinement) VJP (Vapor Jet Printing)depositors according to an embodiment of the disclosed subject matter.

FIG. 5 shows a cross-section of a time stable DEC VJP micronozzle arrayprinting a compound material onto a substrate according to an embodimentof the disclosed subject matter.

FIG. 6 shows a frontal section of a time stable DEC VJP micronozzlearray printing a compound material onto a substrate according to anembodiment of the disclosed subject matter.

FIG. 7 shows streamlines of flow of process gasses for a time stable DECVJP micronozzle array according to an embodiment of the disclosedsubject matter.

FIG. 8 shows a ring of inert convectors around a time stable DEC VJPmicronozzle array according to an embodiment of the disclosed subjectmatter.

FIG. 9 shows a MEMS (Micro-Electro-Mechanical Systems) valve used in atime-variable DEC VJP micronozzle array according to an embodiment ofthe disclosed subject matter.

DETAILED DESCRIPTION

Generally, an OLED comprises at least one organic layer disposed betweenand electrically connected to an anode and a cathode. When a current isapplied, the anode injects holes and the cathode injects electrons intothe organic layer(s). The injected holes and electrons each migratetoward the oppositely charged electrode. When an electron and holelocalize on the same molecule, an “exciton,” which is a localizedelectron-hole pair having an excited energy state, is formed. Light isemitted when the exciton relaxes via a photoemissive mechanism. In somecases, the exciton may be localized on an excimer or an exciplex.Non-radiative mechanisms, such as thermal relaxation, may also occur,but are generally considered undesirable.

The initial OLEDs used emissive molecules that emitted light from theirsinglet states (“fluorescence”) as disclosed, for example, in U.S. Pat.No. 4,769,292, which is incorporated by reference in its entirety.Fluorescent emission generally occurs in a time frame of less than 10nanoseconds.

More recently, OLEDs having emissive materials that emit light fromtriplet states (“phosphorescence”) have been demonstrated. Baldo et al.,“Highly Efficient Phosphorescent Emission from OrganicElectroluminescent Devices,” Nature, vol. 395, 151-154, 1998;(“Baldo-I”) and Baldo et al., “Very high-efficiency green organiclight-emitting devices based on electrophosphorescence,” Appl. Phys.Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), are incorporated byreference in their entireties. Phosphorescence is described in moredetail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporatedby reference.

FIG. 1 shows an organic light emitting device 100. The figures are notnecessarily drawn to scale. Device 100 may include a substrate 110, ananode 115, a hole injection layer 120, a hole transport layer 125, anelectron blocking layer 130, an emissive layer 135, a hole blockinglayer 140, an electron transport layer 145, an electron injection layer150, a protective layer 155, a cathode 160, and a barrier layer 170.Cathode 160 is a compound cathode having a first conductive layer 162and a second conductive layer 164. Device 100 may be fabricated bydepositing the layers described, in order. The properties and functionsof these various layers, as well as example materials, are described inmore detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which areincorporated by reference.

More examples for each of these layers are available. For example, aflexible and transparent substrate-anode combination is disclosed inU.S. Pat. No. 5,844,363, which is incorporated by reference in itsentirety. An example of a p-doped hole transport layer is m-MTDATA dopedwith F₄-TCNQ at a molar ratio of 50:1, as disclosed in U.S. PatentApplication Publication No. 2003/0230980, which is incorporated byreference in its entirety. Examples of emissive and host materials aredisclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which isincorporated by reference in its entirety. An example of an n-dopedelectron transport layer is BPhen doped with Li at a molar ratio of 1:1,as disclosed in U.S. Patent Application Publication No. 2003/0230980,which is incorporated by reference in its entirety. U.S. Pat. Nos.5,703,436 and 5,707,745, which are incorporated by reference in theirentireties, disclose examples of cathodes including compound cathodeshaving a thin layer of metal such as Mg:Ag with an overlyingtransparent, electrically-conductive, sputter-deposited ITO layer. Thetheory and use of blocking layers is described in more detail in U.S.Pat. No. 6,097,147 and U.S. Patent Application Publication No.2003/0230980, which are incorporated by reference in their entireties.Examples of injection layers are provided in U.S. Patent ApplicationPublication No. 2004/0174116, which is incorporated by reference in itsentirety. A description of protective layers may be found in U.S. PatentApplication Publication No. 2004/0174116, which is incorporated byreference in its entirety.

FIG. 2 shows an inverted OLED 200. The device includes a substrate 210,a cathode 215, an emissive layer 220, a hole transport layer 225, and ananode 230. Device 200 may be fabricated by depositing the layersdescribed, in order. Because the most common OLED configuration has acathode disposed over the anode, and device 200 has cathode 215 disposedunder anode 230, device 200 may be referred to as an “inverted” OLED.Materials similar to those described with respect to device 100 may beused in the corresponding layers of device 200. FIG. 2 provides oneexample of how some layers may be omitted from the structure of device100.

The simple layered structure illustrated in FIGS. 1 and 2 is provided byway of non-limiting example, and it is understood that embodiments ofthe invention may be used in connection with a wide variety of otherstructures. The specific materials and structures described areexemplary in nature, and other materials and structures may be used.Functional OLEDs may be achieved by combining the various layersdescribed in different ways, or layers may be omitted entirely, based ondesign, performance, and cost factors. Other layers not specificallydescribed may also be included. Materials other than those specificallydescribed may be used. Although many of the examples provided hereindescribe various layers as comprising a single material, it isunderstood that combinations of materials, such as a mixture of host anddopant, or more generally a mixture, may be used. Also, the layers mayhave various sublayers. The names given to the various layers herein arenot intended to be strictly limiting. For example, in device 200, holetransport layer 225 transports holes and injects holes into emissivelayer 220, and may be described as a hole transport layer or a holeinjection layer. In one embodiment, an OLED may be described as havingan “organic layer” disposed between a cathode and an anode. This organiclayer may comprise a single layer, or may further comprise multiplelayers of different organic materials as described, for example, withrespect to FIGS. 1 and 2.

Structures and materials not specifically described may also be used,such as OLEDs comprised of polymeric materials (PLEDs) such as disclosedin U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated byreference in its entirety. By way of further example, OLEDs having asingle organic layer may be used. OLEDs may be stacked, for example asdescribed in U.S. Pat. No. 5,707,745 to Forrest et al, which isincorporated by reference in its entirety. The OLED structure maydeviate from the simple layered structure illustrated in FIGS. 1 and 2.For example, the substrate may include an angled reflective surface toimprove out-coupling, such as a mesa structure as described in U.S. Pat.No. 6,091,195 to Forrest et al., and/or a pit structure as described inU.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated byreference in their entireties.

Unless otherwise specified, any of the layers of the various embodimentsmay be deposited by any suitable method. For the organic layers,preferred methods include thermal evaporation, ink-jet, such asdescribed in U.S. Pat. Nos. 6,013,982 and 6,087,196, which areincorporated by reference in their entireties, organic vapor phasedeposition (OVPD), such as described in U.S. Pat. No. 6,337,102 toForrest et al., which is incorporated by reference in its entirety, anddeposition by organic vapor jet printing (OVJP), such as described inU.S. Pat. No. 7,431,968, which is incorporated by reference in itsentirety. Other suitable deposition methods include spin coating andother solution based processes. Solution based processes are preferablycarried out in nitrogen or an inert atmosphere. For the other layers,preferred methods include thermal evaporation. Preferred patterningmethods include deposition through a mask, cold welding such asdescribed in U.S. Pat. Nos. 6,294,398 and 6,468,819, which areincorporated by reference in their entireties, and patterning associatedwith some of the deposition methods such as ink-jet and OVJD. Othermethods may also be used. The materials to be deposited may be modifiedto make them compatible with a particular deposition method. Forexample, substituents such as alkyl and aryl groups, branched orunbranched, and preferably containing at least 3 carbons, may be used insmall molecules to enhance their ability to undergo solution processing.Substituents having 20 carbons or more may be used, and 3-20 carbons isa preferred range. Materials with asymmetric structures may have bettersolution processability than those having symmetric structures, becauseasymmetric materials may have a lower tendency to recrystallize.Dendrimer substituents may be used to enhance the ability of smallmolecules to undergo solution processing.

Devices fabricated in accordance with embodiments of the presentinvention may further optionally comprise a barrier layer. One purposeof the barrier layer is to protect the electrodes and organic layersfrom damaging exposure to harmful species in the environment includingmoisture, vapor and/or gases, etc. The barrier layer may be depositedover, under or next to a substrate, an electrode, or over any otherparts of a device including an edge. The barrier layer may comprise asingle layer, or multiple layers. The barrier layer may be formed byvarious known chemical vapor deposition techniques and may includecompositions having a single phase as well as compositions havingmultiple phases. Any suitable material or combination of materials maybe used for the barrier layer. The barrier layer may incorporate aninorganic or an organic compound or both. The preferred barrier layercomprises a mixture of a polymeric material and a non-polymeric materialas described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos.PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporatedby reference in their entireties. To be considered a “mixture”, theaforesaid polymeric and non-polymeric materials comprising the barrierlayer should be deposited under the same reaction conditions and/or atthe same time. The weight ratio of polymeric to non-polymeric materialmay be in the range of 95:5 to 5:95. The polymeric material and thenon-polymeric material may be created from the same precursor material.In one example, the mixture of a polymeric material and a non-polymericmaterial consists essentially of polymeric silicon and inorganicsilicon.

Devices fabricated in accordance with embodiments of the invention canbe incorporated into a wide variety of electronic component modules (orunits) that can be incorporated into a variety of electronic products orintermediate components. Examples of such electronic products orintermediate components include display screens, lighting devices suchas discrete light source devices or lighting panels, etc. that can beutilized by the end-user product manufacturers. Such electroniccomponent modules can optionally include the driving electronics and/orpower source(s). Devices fabricated in accordance with embodiments ofthe invention can be incorporated into a wide variety of consumerproducts that have one or more of the electronic component modules (orunits) incorporated therein. A consumer product comprising an OLED thatincludes the compound of the present disclosure in the organic layer inthe OLED is disclosed. Such consumer products would include any kind ofproducts that include one or more light source(s) and/or one or more ofsome type of visual displays. Some examples of such consumer productsinclude flat panel displays, computer monitors, medical monitors,televisions, billboards, lights for interior or exterior illuminationand/or signaling, heads-up displays, fully or partially transparentdisplays, flexible displays, laser printers, telephones, mobile phones,tablets, phablets, personal digital assistants (PDAs), wearable devices,laptop computers, digital cameras, camcorders, viewfinders,micro-displays (displays that are less than 2 inches diagonal), 3-Ddisplays, virtual reality or augmented reality displays, vehicles, videowalls comprising multiple displays tiled together, theater or stadiumscreen, and a sign. Various control mechanisms may be used to controldevices fabricated in accordance with the present invention, includingpassive matrix and active matrix. Many of the devices are intended foruse in a temperature range comfortable to humans, such as 18 C to 30 C,and more preferably at room temperature (20-25 C), but could be usedoutside this temperature range, for example, from −40 C to 80 C.

The materials and structures described herein may have applications indevices other than OLEDs. For example, other optoelectronic devices suchas organic solar cells and organic photodetectors may employ thematerials and structures. More generally, organic devices, such asorganic transistors, may employ the materials and structures.

In some embodiments, the OLED has one or more characteristics selectedfrom the group consisting of being flexible, being rollable, beingfoldable, being stretchable, and being curved. In some embodiments, theOLED is transparent or semi-transparent. In some embodiments, the OLEDfurther comprises a layer comprising carbon nanotubes.

In some embodiments, the OLED further comprises a layer comprising adelayed fluorescent emitter. In some embodiments, the OLED comprises aRGB pixel arrangement or white plus color filter pixel arrangement. Insome embodiments, the OLED is a mobile device, a hand held device, or awearable device. In some embodiments, the OLED is a display panel havingless than 10 inch diagonal or 50 square inch area. In some embodiments,the OLED is a display panel having at least 10 inch diagonal or 50square inch area. In some embodiments, the OLED is a lighting panel.

In some embodiments of the emissive region, the emissive region furthercomprises a host.

In some embodiments, the compound can be an emissive dopant. In someembodiments, the compound can produce emissions via phosphorescence,fluorescence, thermally activated delayed fluorescence, i.e., TADF (alsoreferred to as E-type delayed fluorescence), triplet-tripletannihilation, or combinations of these processes.

The OLED disclosed herein can be incorporated into one or more of aconsumer product, an electronic component module, and a lighting panel.The organic layer can be an emissive layer and the compound can be anemissive dopant in some embodiments, while the compound can be anon-emissive dopant in other embodiments.

The organic layer can also include a host. In some embodiments, two ormore hosts are preferred. In some embodiments, the hosts used may be a)bipolar, b) electron transporting, c) hole transporting or d) wide bandgap materials that play little role in charge transport. In someembodiments, the host can include a metal complex. The host can be aninorganic compound.

Combination with Other Materials

The materials described herein as useful for a particular layer in anorganic light emitting device may be used in combination with a widevariety of other materials present in the device. For example, emissivedopants disclosed herein may be used in conjunction with a wide varietyof hosts, transport layers, blocking layers, injection layers,electrodes and other layers that may be present. The materials describedor referred to below are non-limiting examples of materials that may beuseful in combination with the compounds disclosed herein, and one ofskill in the art can readily consult the literature to identify othermaterials that may be useful in combination.

Various materials may be used for the various emissive and non-emissivelayers and arrangements disclosed herein. Examples of suitable materialsare disclosed in U.S. Patent Application Publication No. 2017/0229663,which is incorporated by reference in its entirety.

Conductivity Dopants:

A charge transport layer can be doped with conductivity dopants tosubstantially alter its density of charge carriers, which will in turnalter its conductivity. The conductivity is increased by generatingcharge carriers in the matrix material, and depending on the type ofdopant, a change in the Fermi level of the semiconductor may also beachieved. Hole-transporting layer can be doped by p-type conductivitydopants and n-type conductivity dopants are used in theelectron-transporting layer.

HIL/HTL:

A hole injecting/transporting material to be used in the presentinvention is not particularly limited, and any compound may be used aslong as the compound is typically used as a hole injecting/transportingmaterial.

EBL:

An electron blocking layer (EBL) may be used to reduce the number ofelectrons and/or excitons that leave the emissive layer. The presence ofsuch a blocking layer in a device may result in substantially higherefficiencies, and or longer lifetime, as compared to a similar devicelacking a blocking layer. Also, a blocking layer may be used to confineemission to a desired region of an OLED. In some embodiments, the EBLmaterial has a higher LUMO (closer to the vacuum level) and/or highertriplet energy than the emitter closest to the EBL interface. In someembodiments, the EBL material has a higher LUMO (closer to the vacuumlevel) and or higher triplet energy than one or more of the hostsclosest to the EBL interface. In one aspect, the compound used in EBLcontains the same molecule or the same functional groups used as one ofthe hosts described below.

Host:

The light emitting layer of the organic EL device of the presentinvention preferably contains at least a metal complex as light emittingmaterial, and may contain a host material using the metal complex as adopant material. Examples of the host material are not particularlylimited, and any metal complexes or organic compounds may be used aslong as the triplet energy of the host is larger than that of thedopant. Any host material may be used with any dopant so long as thetriplet criteria is satisfied.

HBL:

A hole blocking layer (HBL) may be used to reduce the number of holesand/or excitons that leave the emissive layer. The presence of such ablocking layer in a device may result in substantially higherefficiencies and/or longer lifetime as compared to a similar devicelacking a blocking layer. Also, a blocking layer may be used to confineemission to a desired region of an OLED. In some embodiments, the HBLmaterial has a lower HOMO (further from the vacuum level) and or highertriplet energy than the emitter closest to the HBL interface. In someembodiments, the HBL material has a lower HOMO (further from the vacuumlevel) and or higher triplet energy than one or more of the hostsclosest to the HBL interface.

ETL:

An electron transport layer (ETL) may include a material capable oftransporting electrons. The electron transport layer may be intrinsic(undoped), or doped. Doping may be used to enhance conductivity.Examples of the ETL material are not particularly limited, and any metalcomplexes or organic compounds may be used as long as they are typicallyused to transport electrons.

Charge Generation Layer (CGL)

In tandem or stacked OLEDs, the CGL plays an essential role in theperformance, which is composed of an n-doped layer and a p-doped layerfor injection of electrons and holes, respectively. Electrons and holesare supplied from the CGL and electrodes. The consumed electrons andholes in the CGL are refilled by the electrons and holes injected fromthe cathode and anode, respectively; then, the bipolar currents reach asteady state gradually. Typical CGL materials include n and pconductivity dopants used in the transport layers.

Embodiments of the disclosed subject matter may provide OLED (organiclight emitting device) encapsulation by alternating deposition channelsin a Confined Organic Printing (COP) type device to produce aluminumoxide. This may be similar to forming an atomic deposition layer (ALD).Because of the small size of the deposition channels and the isolationbetween channels, a growth rate may be very rapid. This may address oneof the biggest problems for ALD encapsulation, which is slow growthrate. Using the micro-CVD (chemical vapor deposition) printing aperturesystem discussed throughout, encapsulation may be used to form featuresand/or cover defects or particles on a device, a display, or the like.

Embodiments of the disclosed subject matter may provide localencapsulation. For example, ALD or multi-layer stack (that may be, forexample, organic, inorganic, ALD, a combination thereof, or the like)over selective areas of a display and/or device to add specific strengthto local areas. For example, the ALD and/or multi-layer stack may beadded along the fold region of a foldable OLED display. Micro-ALD ormicro-ALE (atomic layer epitaxy) may provide close spacing of depositionchannels to provide a high growth rate.

High aluminum content Group III-nitride materials may be difficult togrow rapidly due to gas phase interaction between trimethyl aluminum andammonia. In embodiments of the disclosed subject matter, using adepositor-exhaust-confinement type (DEC-type) showerhead, extremely highgrowth rates may be achieved, which may be beneficial for forming deepultraviolet light emitting devices (e.g., for purification purposes).

Embodiments of the disclosed subject matter may provide selective areadeposition by micro CVD. A DEC-type print aperture may be used to printmaterials in the same manner as ink jet, but using CVD materials andtechnique (e.g., by using cold gas and a hot substrate). This could beused, for example to “print” optical elements on silicon devices.Although some initiatives have attempted to do this with bulk films,small structures may be easier to grow using lattice mis-matchedmaterials.

Implementations of the disclosed subject matter may be used to formorganic TFTs (thin film transistors) for display backplanes, where itmay be desirable to cover a small portion of the pixel area. Embodimentsof the disclosed subject matter may also use Plasma Enhanced ChemicalVapor Deposition (PECVD), or micro PECVD.

Embodiments of the disclosed subject matter may provide additivedeposition of thin films of different materials to form and/or build upthree-dimensional (3D) stacks. Locally deposited thin films may be usedto repair holes and/or other defects in existing films.

Some prior systems, such as described in U.S. Patent Publn. No.2016/0068953, require separate pressure gages and controllers for eachexhaust channel. In contrast, embodiments of the disclosed subjectmatter provide configurations with small dimensions that are controlledby flow restriction in the exhaust channels.

In some embodiments, a similar concept to those described above may beused for Group III-V epitaxy, where TMA (trimethyl aluminum) may reactwith ammonia in the gas phase. The highest quality material and fastestgrowth rates may be achieved when TMA and NH₃ do not mix in the gasphase.

Group III-V materials may be separated in the delivery system that mayinclude a “showerhead.” Typically, the Group III and Group V materialsmay mix in the gas space between the showerhead and substrate. For AlN,the TMA and NH₃ may react in the gas phase to form adducts, which mayreduce the growth rate (as it consumes TMA) and creates particles.Injecting TMA and NH₃ in separate regions minimizes the issue ofreduction in growth rate. Using DEC, such a reduction in growth rate maybe eliminated.

There may be applications where it is desirable to accurately deposit orprint thin films on a specific location on a substrate. Vapor jetprinting may lower printing costs by applying materials in a particularlocation, as opposed to coating a complete substrate. The use of a smallmonolithic printing head assembly may reduce heating from a hot printinghead to a substrate, which can avoid damage to devices already depositedon to the substrate. This is because in VJP or spatial ALD (atomic layerdeposition), source-to-substrate distances may be less than 1 mm, so ifa large print head is heated to high temperatures (e.g., 300° C.) andplaced less than 1 mm from a substrate for a plurality of seconds, thesubstrate surface may heat.

The use of DEC print heads may enable the deposition of films that usedifferent source gases that react at, or close to, a deposition site.For example, in ALD, a first gas may be placed on a substrate for amonolayer deposition. When the first gas is removed and a second gas isapplied to the same location, a monolayer growth may occur when thesecond gas reacts with the surface layer deposited from the first gas.These operations may be repeated to build up monolayers of film. SpatialALD may benefit from DEC VJP technology to avoid mixing of gases priorto the gasses meeting at the growth site. Use of a monolithic print headmay provide pinpoint and/or line deposition over one or more selectiveareas of a substrate to avoiding wasting material.

The two gases may be introduced to the growing surface by severalapproaches. Firstly, multiple heads may be used, each jetting adifferent gas and aligned such that a nozzle from one jet head emittinggas A is aligned with a nozzle from a second jet head emitting gas B.The growing surface may experience a series of ABAB gas exposures togrow an ALD film. A second approach may have one jet head withalternating ABABAB nozzles confined from each other. The substrate orprint head may be moved a distance corresponding to the nozzle spacing,so the second source gas may reach the growing surface. The assembly maythen may be moved back to have the first source gas jetted on to thegrowing surface. In some embodiments, a plurality of alternating nozzlesmay be stacked to yield a desired film thickness on one printing pass.The number of pairs of nozzles may be equal to a film thickness dividedby the bi-layer atom thickness. A third approach could be to have thegases coming out of the nozzle switched at the source to create an ABABgrowth pattern on the substrate surface. The advantages of usingmonolithic assembly VJP for spatial ALD is that the small volumesinherent in VJP may provide fast purging times and deposition rates,unlike conventional ALD where the purging times to remove one gas beforeanother is introduced lead to low deposition rates. Another advance ofusing monolithic assembly VJP for spatial ALD is for high utilization ofmaterial. Both of these features may reduce production costs.

Many devices, particularly organic devices such as OLEDs, solar cells,and transistors, may be sensitive to air and moisture, and thin filmbarrier films may be deposited on such devices to provide isolation. Onesuch encapsulation approach may use ALD, as described above. For OLEDs,a multi-layer system having dyads or pairs of alternating films may beused, where one film is organic and one film is inorganic. In someembodiments, a single layer barrier with both organic and inorganicproperties in the same film may be used. The approaches described abovemay be used to produce a multi-layer system with nozzle A producing adeposition, for example, of inorganic barrier film, and a second nozzleB producing an organic film. Using one of the three operations discussedabove, a multi-layer film may be grown. This may rely on CVD or remoteplasma PECVD processes for individual film deposition.

As ALD encapsulation may have very high quality, one approach may be tocoat an OLED with a blanket thin film encapsulation, and then apply anALD based system locally using VJP in regions where it is desirable tohave a very high quality film, such as for a foldable AMOLED display,along the region which will undergo repetitive folding.

Vapor deposition of III-V materials such as GaAs, AlAs, InGaAs, InP,InGaAlP, GaN, AlGaN, GaInN, and AlN may be deposited using showerheads.The Group III materials and Group V materials may have separate gaspathways. The Group III and Group V materials mix in the gas phasebetween the vapor injector and heated substrate. Trimethyl aluminum isparticularly reactive with the Group V precursors (e.g., arsine,phosphine, or ammonia) and may react in the gas space between thesubstrate and gas injector. Any adducts formed may reduce the efficiencyof material utilization and may produce particulates if the adducts growto sufficient size. In the case of AlN, the adduct formation may limitthe growth rate of AlN to less than 1 μm/hour. In some depositionsystems, increasing the flow of TMA may reduce the growth rate due to anincrease in the rate of adduct formation. In one embodiment, theformation of adducts may be minimized by adding a purge flow between theTMA and NH₃ injectors to minimize gas phase mixing.

Using DEC print heads for Group III-V epitaxy may eliminate the issue ofefficiency of material utilization and the production of particulates.Gas phase mixing may be eliminated by the introduction of exhaustchannels adjacent to each deposition channel and adding a confinementchannel between exhaust channels. The sequence of channels may be:C-E-TMA-E-C-E-NH3-E (where C=Confinement, and E=Exhaust). This sequencemay be repeated a plurality of times to increase growth rate in a linearsystem, or may be spaced radially in the case of a showerhead-typesystem with a rotating susceptor.

Chemical vapor deposition (CVD) processes and plasma assisted CVD may beapplied to local regions of a substrate using gases ejected from nozzlesof a VJP system. Advantages of this arrangement may include highmaterial utilization by particular coating regions of need.

CVD is a chemical process that may be used to produce high quality,high-performance, solid materials. The process may be used in thesemiconductor industry to produce thin films. In typical CVD, the wafer(substrate) may be exposed to one or more volatile precursors, whichreact and/or decompose on the substrate surface to produce the desireddeposit. Frequently, volatile by-products are also produced, which maybe removed by gas flow through the reaction chamber.

Microfabrication processes may use CVD to deposit materials in variousforms, including: monocrystalline, polycrystalline, amorphous, andepitaxial. These materials may include: silicon (e.g., SiO₂, germanium,carbide, nitride, oxynitride), carbon (e.g., carbon fiber, nanofibers,nanotubes, diamond, and graphene), fluorocarbons, filaments, tungsten,titanium nitride and various high-k dielectrics.

CVD may be performed in a variety of process formats. These processesgenerally differ in how the chemical reactions may be initiated. Forexample, CVD may be classified by the type of substrate heating, such ashot wall CVD, in which the chamber is heated by an external power sourceand the substrate is heated by radiation from the heated chamber walls.With another type of substrate heading, such as cold wall CVD, thesubstrate may directly heated either by induction or by passing currentthrough the substrate itself or a heater in contact with the substrate.The chamber walls may be at room temperature.

CVD may be classified by the type of plasma processing used. Forexample, CVD may be classified as microwave plasma-assisted CVD (MPCVD).CVD may be classified as Plasma-Enhanced CVD (PECVD), which may utilizeplasma to enhance chemical reaction rates of the precursors. PECVDprocessing may allow for deposition at lower temperatures, which may bebeneficial in the manufacture of semiconductors. The lower temperaturesmay allow for the deposition of organic coatings, such as plasmapolymers, that have been used for nanoparticle surfacefunctionalization. CVD may also be classified as remote plasma-enhancedCVD (RPECVD), which may be similar to PECVD except that the wafersubstrate is not directly in the plasma discharge region. RPECVD mayinclude removing the wafer from the plasma. This approach may enablemicro PECVD using VJP, given the very small dimensions of the system,which may not allow a plasma to be struck between ejection nozzle andsubstrate.

Three-dimensional (3D) printing, which may be used to fabricate 3Dstructures, is based on printing a range of materials from a liquidform. VJP may be used to form complex 3D structures having a pluralityof materials deposited from a vapor, as opposed to liquid form. Suchmaterials could be organic, metallic, dielectric, or the like. Stacks ofalternating materials may not be limited to similar materials, such asinorganics on top of inorganics (ALD of Al₂O₃). Organics may bedeposited on top of inorganics, metals, or oxides to form compositemulti-layer structures.

Large area devices may often have defects arising from particulates. Fororganic devices which are very sensitive to the environment, any pinholes in the thin film encapsulation barrier protecting them fromambient conditions may lead to black spots and degradation of theorganic devices. Encapsulation films deposited by VJP may be used theseal any pin-holes when they are detected. Detection and encapsulationmay be performed locally relatively quickly, without needing to coat thewhole device area. If a defect or black spot is detected from a testwhere all pixels of a device are illuminated, the location of the defector black spot may be noted and the device may be placed into a VJPchamber and the jet head placed over the detected defective area tore-seal it and prevent further degradation. This may increase the yieldof fabricating very large area devices, where the probability of defectsand/or pin holes becomes significant and the cost of rejecting a deviceor display is also high, making repair desirable. This approach may beused with any device having pin holes and/or defects in a thin filmbarrier layer.

An array of patterned thin film features comprised of compound materialformed from reactive gas precursors may be deposited by VJP using a gridof isolated convective cells. Each convective cell may include one ofthe relevant precursors, and may be isolated from its neighbors. Thecompound material may be a Group III-V semiconductor or a Group II-VImaterial grown in a manner analogous to MOCVD or ALD, respectively. VJPmay be differentiated from these techniques primarily by the capabilityof printing pinpoint features without the use of shadow masks orsubtractive patterning. Other material sets may be possible for VJP, andany solid material that can be formed from two or more vaporizedprecursors may be used.

Organic Vapor Jet Printing (OVJP) may utilize a carrier gas to transportorganic material from a heated source container to the print nozzleassembly which is in close proximity to a substrate. The nozzle assemblythen forms the organic vapor into jets that condense onto well-definedzones of the substrate, allowing patterns to be generated in theresulting film. A micronozzle array, such as disclosed in U.S. PatentPubln. No. 2015/0376787, incorporated by reference herein, may utilize acombination of deposition apertures surrounded by exhaust apertures anda gas confinement flow to confine the line width and overspray. Thisarrangement may be referred to as DEC (Deposition-Exhaust-Confinement).

Overspray may be eliminated by using a flow of confinement gas toprevent the diffusion and transport of organic material away from adesired deposition region. Preferably, a chamber pressure range of 50 to300 Torr may be used. FIGS. 3A-3B show an OVJP depositor, and amicronozzle array on which one or more OVJP depositors are arranged. Adepositor design, shown from the perspective of the substrate in FIG.3A, may include one or more rectangular delivery apertures 301 locatedbetween a pair of exhaust apertures 302. The flow through the deliveryapertures 301 may include organic vapor entrained in an inert deliverygas. The exhaust apertures 302 may withdraw gas from the region underthe depositor at a mass flow rate exceeding the delivery flow. Theexhaust apertures 302 may remove the delivery flow and any surplusorganic vapor entrained within it, as well as a balance of confinementgas drawn from the ambient surrounding the depositor. Delivery apertures301 and exhaust apertures 302 may be separated by a width of a DE(Deposition-Exhaust) spacer 303. Delivery apertures 301 and exhaustapertures 302 may be arranged so that the long axes are parallel to thedirection of printing 304. A solid section called the flow retarder 305may be positioned between the delivery apertures 301 to modulate thedelivery gas flux profile impinging onto the substrate (e.g., substrate314 shown in FIG. 3B).

Depositors 306 may be arranged linearly on a micronozzle array 307, sothat each depositor may border another on at least one of its sideboundaries 308. The top and bottom edges 309 of the depositor aredefined by the edges of a linear micronozzle array (e.g., micronozzlearray 307 shown in FIG. 3A). Distribution channels 310 placed betweendepositors 306 may provide a source of confinement gas along the sidesof each of the depositors 306. Alternately, confinement gas may flow infrom the edges of the depositors 306, particularly if these channels areomitted. Micronozzle array 307 may be configured to minimize crosstalkbetween depositors 306 so that multiple printed features are as close toidentical as possible across the width of the depositor array (e.g., thearray of depositors 306 of the micronozzle array 307).

FIG. 3B shows a cross-section of a depositor (e.g., one of thedepositors 306 shown in FIG. 3A). The channels shown in FIG. 3B may beetched into silicon and sealed on the top and bottom by wafer bondingtechniques. Delivery channels 311 may carry organic vapor laden deliverygas to delivery apertures 301 that are surrounded on each side byexhaust apertures 302. The exhaust apertures 302 may connect to exhaustchannels 312 that may remove excess vapor from the desired printing zone315. Confinement gas may be fed into the sides of the depositor by thedistribution channels 310. The confinement gas may sweep inward throughthe gap 313 created between the depositor and the substrate 314. Theinward sweep of confinement gas driven by negative pressure at theexhaust aperture may prevent the flow of organic vapor laden gas fromthe delivery aperture from migrating beyond the desired printing zone315. Organic vapor from the delivery aperture may adsorb to thesubstrate 314 within the printing zone to produce a well-defined thinfilm feature with no overspray beyond it.

FIG. 4 shows a section of a micronozzle array having a time-stable DECVJP depositors according to an embodiment of the disclosed subjectmatter. Depositors 401 may deposit reactant A, and depositors 402 maydeposit reactant B. Each depositor 401, 402 may create a convective cellover the substrate. Depositors 401, 402 may be arranged in rows 403 ofalternating depositor types with dispersed confinement gas sources 404located between adjacent rows.

FIG. 5 shows a cross-section of a time stable DEC VJP micronozzle arrayprinting a compound material onto a substrate according to an embodimentof the disclosed subject matter. A depositor array 501 having printheads and substrate 502 are show cross section in FIG. 5 parallel to theplane of the substrate 502 and perpendicular to the direction of motion502 a. If the depositor array 501 is moved linearly with respect to asubstrate 502, discrete lines of deposition may form, corresponding tothe rows on the print head. As the substrate 502 moves relative to thedepositors, the printed zones on the substrate 502 may alternate betweenexposure to rows of convective cells 503 to deposit reactant A andconvective cells 504 to deposit reactant B. This may result in thebuildup of an ordered compound material 505.

FIG. 6 shows a frontal section of a time stable DEC VJP micronozzlearray printing a compound material onto a substrate according to anembodiment of the disclosed subject matter. The print head and substrateare illustrated in cross-section transverse to the direction ofsubstrate motion. Each column of depositors 601 (orthogonal to rows) maycorrespond to a line of compound material 602. Confinement flow may bedistributed between adjacent rows of depositors by porous tracks 603 inthe print head that run parallel to the direction of substrate motion.

FIG. 7 shows streamlines of flow of process gasses for a time stable DECVJP micronozzle array according to an embodiment of the disclosedsubject matter. That is, convective cells generated by the print headare shown in FIG. 7. The cells are arranged in a two-dimensional grid.In this particular configuration, rows 701 contain cells of vapor A androws 702 contain cells of vapor B. In one configuration, depositors ofvarying types may be arranged in a checkerboard configuration.Confinement gas may be distributed through rows of nozzles 703 that runorthogonally to the rows 701, 702 of like material depositors. Apositive pressure (relative to a chamber pressure) feed of confinementgas may be used to maintain uniformity for this ALD-VJP structure, sinceconfinement gas may be evenly distributed to depositors that may beseveral rows deep within an array and do not share a perimeter with thechamber ambient.

The streamlines 704 generated by each depositor 705 may not cross intoneighboring depositors. This may indicate that each depositor and theconvective cell within it are isolated from its neighbors. A high levelof uniformity between depositors may be obtained by a repeating array,since uniformity is equivalent to two-dimensional periodic symmetry inthis context.

FIG. 8 shows a ring of inert convectors around a time stable DEC VJPmicronozzle array according to an embodiment of the disclosed subjectmatter. As shown in FIG. 8, inert convectors 801 may surround theperimeter of a micro-nozzle array containing depositors jettingprecursors 802 (precursor A) and precursor 803 (precursor B) to minimizeedge effects. These inert convectors 801 may have exhaust andconfinement flows but the delivery flow like depositors, if present, maynot contain any reactive vapor.

Micro-valves can be monolithically integrated into a VJP depositor arrayas described in U.S. patent application Ser. No. 16/243,393 filed Jan.9, 2019, incorporated by reference herein, in its entirety. In additionto switching flow on and off, the valves can switch the source of flowfeeding the delivery aperture between two sources of dissimilar vapor.FIG. 9 shows a MEMS (Micro-Electro-Mechanical Systems) valve used in atime-variable DEC VJP micronozzle array according to an embodiment ofthe disclosed subject matter. In particular, an example of a depositorwithin a valved print head is shown in a cross-section in FIG. 9. Twoplug valves 901, 902 may be separated from their surrounding channels903 by etching. The plug valves 901, 902 may be connected to thesidewalls of the channels 904 by flexures 905. The plug valves 901, 902may be actuated by pushrods attached to the far ends of stems 906 thatmay be actuated by a piezoelectric array. A central channel 907 may feeda continuous stream of inert delivery gas that is not laden with areactive vapor.

The left hand channel (i.e., the channel to the left of central channel907) with a micro-valve (e.g., plug valve 901) may carry delivery gaswith reactive species A. The right hand channel (i.e., the channel tothe right of central channel 907) may carry delivery gas with reactivespecies B. When the left hand stem 906 is depressed and the right handvalve (e.g., plug valve 902 for the channel to the right of centralchannel 907) is not depressed, as shown in FIG. 9, vapor containingspecies B flows downward to the delivery aperture 908. Vapor withspecies A flows through the delivery aperture when the valve positionsare reversed (i.e., when plug valve 902 is closed and plug valve 901 isopen). Both stems 906 may be depressed so vapor flow from both channelsis blocked by the plug valves 901, 902. This may be done to purge thedelivery plenum 909 so that species A and B do not react within it. Afeature made from compound material may be deposited by repeatedlycycling the valves 901, 902 (i.e., alternating the opening and closingof each valve independently) so that species A is jetted from thedelivery aperture 908, then the delivery aperture 908 is purged, thenspecies B is jetted form the delivery aperture 908, and the deliveryaperture 908 is again purged, at which point the cycle repeats.

The depositor may include other features of the DEC depositor asdiscussed above. The delivery aperture may be flanked on both sides byexhaust channels 910 that remove unreacted vapor from the depositionzone. The confinement channels previously discussed may be replaced with“scallop” type transverse channels 911 that extend through the thicknessof the micronozzle array and draw confinement gas from the chamberambient. Due to the greater internal complexity of this structure, itmay be more practical to arrange depositors abreast as shown in FIGS.3A-3B, as opposed to in a two dimensional array as shown in FIG. 4.Since a single depositor can alternate material types, it may not benecessary to overfly a feature with multiple depositors. An advantage ofa time-variable print head is that it may allow discontinuous featuresto be printed. Features printed by a time-stable print head may beginand end in the runout zone of the substrate. Otherwise, the beginningand end portions of the feature will be thinner than the centralportions, since fewer depositors will pass over them. Another advantageof a time-variable print head is that the use of microvalves and closecoupled exhaust may permit the switching of precursors with very smalltime constants. Since the growth rate is often limited by the timeneeded to switch between precursors for each atomic layer, this maygreatly increase the overall deposition rate. Due to the very smallvolume of the delivery plenum, up to 3,000 complete cycles per second ofA and B deposition, with intra-cycle purges, may be possible.

As shown in FIGS. 3A-9 and described above, a film (e.g., compoundmaterial 505, 605 shown in FIGS. 5-6) may be formed on a selective areaof a substrate (e.g., substrate 502 shown in FIGS. 5-6). A first jet ofa first material may be ejected from a first nozzle assembly (e.g.,depositor 401 shown in FIG. 4, and/or convective cell 503 shown in FIG.5 may eject reactant A) of a jet head comprising a plurality of nozzleassemblies to form a first portion of a film deposition on thesubstrate. A second jet of a second material may be ejected from asecond nozzle assembly (e.g., depositor 402 shown in FIG. 4, and/orconvective cell 504 shown in FIG. 5 may eject reactant B) of theplurality of nozzle assemblies, the second nozzle assembly being alignedwith the first nozzle assembly parallel to a direction of motion betweenthe plurality of nozzle assemblies and the substrate, and the secondmaterial being different than the first material. The second materialmay react with the first portion of the film deposition to form acomposite film deposition (e.g., compound material 505 shown in FIG. 5,and/or compound material 602 shown in FIG. 6) on the substrate whenusing reactive gas precursors.

Each nozzle of the plurality of nozzle assemblies may include jettingapertures (e.g., delivery aperture 301 shown in FIG. 3), exhaustapertures (e.g., exhaust apertures 302 shown in FIG. 3), and confinementapertures (e.g., distribution channels 310 shown in FIG. 3), and ajetting flow ejected from the jetting apertures may be perpendicular tothe substrate, and a confinement flow ejected from the confinementapertures may be parallel to the substrate. A shape and a thicknessprofile of the composite film deposition, and the selective area of thesubstrate upon which the composite film deposition is formed, may bebased on a size and shape of the first nozzle assembly and the secondnozzle assembly, and a distance between the jet head and the substrate.

The selective area of the substrate upon which the composite filmdeposition is formed may be less than 50% of the surface area of thesubstrate, and may be less than 10% of the surface area of thesubstrate. For example, the compound material 602 s shown in FIG. 6 maybe less than 50% of the surface area of the substrate 502. A size of thejet head may be less than 10% of a surface area of the substrate. Forexample, the size of each of the convective cells 503, 504 shown in FIG.5 and/or the depositors 601 shown in FIG. 6 may be less than 10% of thesurface area of the substrate 502. At least one of a length and widthdimension of the jet head may be less than 25% of at least one of alength and width dimension of the substrate. As shown in FIGS. 5-6, thesize of each of the convective cells 503, 504 and/or the depositors 601may be less than 25% of the surface area of the substrate 502. Thedistance between the substrate and the jet head may be 10-100 μm, butmay extend up to 1 mm for low resolution printing applications.

The composite film deposition (e.g., compound material 505 shown in FIG.5, and/or compound material 602 shown in FIG. 6) may include at leastone of an inorganic film, a metal film, and an organic film. Thecomposite film deposition may be formed by using at least one of anatomic layer deposition (ALD), an atomic layer epitaxy (ALE), a chemicalvapor deposition (CVD), plasma enhanced chemical vapor deposition(PECVD), and remote plasma enhanced chemical vapor deposition (RPECVD).The composite film deposition may form a multi-layer barrier film overat least a portion an organic light emitting device (OLED). Thecomposite film deposition may include at least one of Group III-Vmaterials. The Group III-V materials may be deposited using a showerheadhaving separate gas pathways for the Group III materials and the Group Vmaterials. The composite film deposition may be formed from at least oneof GaAs, AlAs, InGaAs, InP, InGaAlP, GaN, AlGaN, GaInN, and AN. Thecomposite film deposition may be a three-dimensional structure of atleast one material selected from an organic material, an inorganicmaterial, a metallic material, and a dielectric material. The compositefilm deposition may be a spatially-localized thin film transistor, alight emitting device, or an organic light emitting device.

One or more surface features may be detected, where the composite filmdeposition (e.g., compound material 505 shown in FIG. 5, and/or compoundmaterial 602 shown in FIG. 6) is formed on the one or more detectedsurface features of the device. One of the detected surface features maybe a surface defect.

In some embodiments, films (e.g., compound material 505, 605 shown inFIGS. 5-6) may be deposited on a selective area of a substrate (e.g.,substrate 502 shown in FIGS. 5-6) that rely on different source gasesthat react at or close to a deposition site (e.g., desired printing zone315 shown in FIG. 3B). A first jet of a first material may be ejectedfrom a first nozzle assembly (e.g., depositor 401 shown in FIG. 4,and/or convective cell 503 shown in FIG. 5 may eject reactant A) of ajet head that is separate from a second nozzle assembly (e.g., depositor402 shown in FIG. 4, and/or convective cell 504 shown in FIG. 5 mayeject reactant B) of the jet head. On a surface of the substrate (e.g.,substrate 502 shown in FIGS. 5-6), a first layer deposition may beformed using the first material. The substrate or the jet head may bemoved a distance (e.g., in direction 502 a shown in FIG. 5)corresponding to a spacing between the first nozzle assembly and thesecond nozzle assembly. A second jet of a second material may be ejectedfrom the second nozzle assembly (e.g., depositor 402 shown in FIG. 4,and/or convective cell 504 shown in FIG. 5 may eject reactant B) of thejet head. The second nozzle assembly may be aligned with the firstnozzle assembly parallel to a direction of motion (e.g., direction 502 ashown in FIG. 5) between the plurality of nozzle assemblies and thesubstrate. The second material may react with the first portion of thefilm deposition to form a composite film deposition (e.g., compoundmaterial 505 shown in FIG. 5, and/or compound material 602 shown in FIG.6) on the substrate when using reactive gas precursors.

The first nozzle assembly and the second nozzle assembly may be confinedfrom one another. Each nozzle of a plurality of nozzle assemblies of thejet head may include jetting apertures (e.g., delivery aperture 301shown in FIG. 3), exhaust apertures (e.g., exhaust apertures 302 shownin FIG. 3), and confinement apertures (e.g., distribution channels 310shown in FIG. 3), and a jetting flow ejected from the jetting aperturesmay be perpendicular to the substrate (e.g., substrate 502 shown inFIGS. 5-6), and a confinement flow ejected from the confinementapertures may be parallel to the substrate. A shape and a thicknessprofile of the composite film deposition, and the selective area of thesubstrate upon which the composite film deposition is formed, may bebased on a size and shape of the first nozzle assembly and the secondnozzle assembly, and a distance between the jet head and the substrate.

The substrate or the jet head may be moved the distance (e.g., indirection 502 a shown in FIG. 5) corresponding to the spacing betweenthe first nozzle assembly and the second nozzle assembly (e.g., thespace between depositors 401 and 402 shown in FIG. 4, or the spacebetween convective cell 503 and convective cell 504 shown in FIG. 5).The composite film deposition (e.g., compound material 505 shown in FIG.5, and/or compound material 602 shown in FIG. 6) may be added to usingthe first material that is emitted from the first nozzle assembly (e.g.,depositor 401 shown in FIG. 4, and/or convective cell 503 shown in FIG.5).

The first nozzle assembly (e.g., depositor 401 shown in FIG. 4, and/orconvective cell 503 shown in FIG. 5) and the second nozzle assembly(e.g., depositor 402 shown in FIG. 4, and/or convective cell 503 shownin FIG. 5) may form a nozzle assembly pair, where a number of nozzleassembly pairs of the plurality of nozzle assemblies may be equal to afilm thickness divided by a bi-layer atom thickness.

In some embodiments, a film (e.g., compound material 505, 605 shown inFIGS. 5-6) may be deposited on a selective area of an object (e.g.,substrate 502 shown in FIGS. 5-6, or a device), where there is switchingbetween a source for a first gas (e.g., reactant A that may be ejectedfrom depositor 401 shown in FIG. 4, and/or convective cell 503 shown inFIG. 5) and a second gas (e.g., reactant B may be ejected by depositor402 shown in FIG. 4, and/or convective cell 504 shown in FIG. 5). Thefirst gas may be ejected from a first nozzle assembly (e.g., depositor401 shown in FIG. 4, and/or convective cell 503 shown in FIG. 5) of ajet head having a plurality of nozzle assemblies, and the second gas maybe ejected from a second nozzle assembly (e.g., depositor 402 shown inFIG. 4, and/or convective cell 504 shown in FIG. 5) of the jet head,where the second nozzle assembly is aligned with the first nozzleassembly parallel to a direction of motion between the plurality ofnozzle assemblies and the object. On a surface of the object, acomposite film deposition (e.g., compound material 505 shown in FIG. 5,and/or compound material 602 shown in FIG. 6) may be formed byalternating the exposure of the surface of the object to the first gasand the second gas by the switching, where the composite film depositionis formed using reactive gas precursors.

It is understood that the various embodiments described herein are byway of example only, and are not intended to limit the scope of theinvention. For example, many of the materials and structures describedherein may be substituted with other materials and structures withoutdeviating from the spirit of the invention. The present invention asclaimed may therefore include variations from the particular examplesand preferred embodiments described herein, as will be apparent to oneof skill in the art. It is understood that various theories as to whythe invention works are not intended to be limiting.

1. A method of depositing a film on a selective area of a substrate, themethod comprising: ejecting a first jet of a first material from a firstnozzle assembly of a jet head comprising a plurality of nozzleassemblies to form a first portion of a film deposition on thesubstrate; and ejecting a second jet of a second material from a secondnozzle assembly of the plurality of nozzle assemblies, the second nozzleassembly being aligned with the first nozzle assembly parallel to adirection of motion between the plurality of nozzle assemblies and thesubstrate, and the second material being different than the firstmaterial, wherein the second material reacts with the first portion ofthe film deposition to form a composite film deposition on the substratewhen using reactive gas precursors, and wherein the composite filmdeposition includes at least one from the group consisting of: aninorganic film, and an organic film.
 2. The method of claim 1, whereinthe inorganic or organic films are semiconducting films.
 3. The methodof claim 2, wherein the composite film deposition comprises at least oneof Group III-V materials.
 4. The method of claim 3, wherein the Groupmaterials are deposited using a showerhead having separate gas pathwaysfor the Group III materials and the Group V materials.
 5. The method ofclaim 2, wherein the composite film deposition is formed from at leastone of the materials selected from the group consisting of: GaAs, AlAs,InGaAs, InP, InGaAlP, GaN, AlGaN, GaInN, and AlN.
 6. A device to deposita film on a selective area of a substrate, the device comprising: a jethead having a plurality of nozzle assemblies, comprising: a first nozzleassembly to eject a first jet of a first material to form a firstportion of a film deposition on the substrate; and a second nozzleassembly to eject a second jet of a second material, the second nozzleassembly being aligned with the first nozzle assembly parallel to adirection of motion between the plurality of nozzle assemblies and thesubstrate, and the second material being different than the firstmaterial, wherein the second material reacts with the first portion ofthe film deposition to form a composite film deposition on the substratewhen using reactive gas precursors, and wherein the composite filmdeposition includes at least one from the group consisting of: aninorganic film, and an organic film.
 7. The device of claim 6, whereinthe inorganic or organic films are semiconducting films.
 8. The deviceof claim 6, wherein each nozzle of the plurality of nozzle assemblies iscomprised of jetting apertures, exhaust apertures, and confinementapertures, and a jetting flow ejected from the jetting apertures isperpendicular to the substrate, and a confinement flow ejected from theconfinement apertures is parallel to the substrate.
 9. The device ofclaim 8, further comprising: a deposition channel in each of theplurality of print head assemblies that is in fluid communication withthe jetting apertures; exhaust channels, in fluid communication with theexhaust apertures, disposed adjacent to each deposition channel; andconfinement channels, in fluid communication with the confinementapertures, disposed between the exhaust channels.
 10. (canceled)
 11. Thedevice of claim 6, wherein the plurality of nozzle assemblies that ejectthe first material and the second material are surrounded by a perimeterof inert convectors that do not emit reactive gasses.
 12. A method ofdepositing films on a selective area of a substrate that rely ondifferent source gases that react at or close to a deposition site, themethod comprising: ejecting a first jet of a first material from a firstnozzle assembly of a jet head that is separate from a second nozzleassembly of the jet head; forming, on a surface of the substrate, afirst layer deposition using the first material; moving the substrate orthe jet head a distance corresponding to a spacing between the firstnozzle assembly and the second nozzle assembly; and ejecting a secondjet of a second material from the second nozzle assembly of the jethead, wherein the second nozzle assembly is aligned with the firstnozzle assembly parallel to a direction of motion between the pluralityof nozzle assemblies and the substrate, wherein the second materialreacts with the first portion of the film deposition to form a compositefilm deposition on the substrate when using reactive gas precursors, andwherein the composite film deposition includes at least one from thegroup consisting of: an inorganic film, and an organic film.
 13. Themethod of claim 12, wherein the first nozzle assembly and the secondnozzle assembly are confined from one another, and wherein each nozzleof a plurality of nozzle assemblies of the jet head is comprised ofjetting apertures, exhaust apertures, and confinement apertures, and ajetting flow ejected from the jetting apertures is perpendicular to thesubstrate, and a confinement flow ejected from the confinement aperturesis parallel to the substrate.
 14. The method of claim 12, wherein ashape and a thickness profile of the composite film deposition, and theselective area of the substrate upon which the composite film depositionis formed, is based on a size and shape of the first nozzle assembly andthe second nozzle assembly, and a distance between the jet head and thesubstrate.
 15. The method of claim 12, further comprising: moving thesubstrate or the jet head the distance corresponding to the spacingbetween the first nozzle assembly and the second nozzle assembly; andadding to the composite film deposition using the first material that isemitted from the first nozzle assembly.
 16. The method of claim 12,wherein the first nozzle assembly and the second nozzle assembly form anozzle assembly pair, wherein a number of nozzle assembly pairs of theplurality of nozzle assemblies is equal to a film thickness divided by abi-layer atom thickness.
 17. The method of claim 12, wherein theselective area of the substrate upon which the composite film depositionis formed is selected from the group consisting of: less than 50% of thesurface area of the substrate, and less than 10% of the surface area ofthe substrate. 18-20. (canceled)
 21. The method of claim 12, wherein thecomposite film deposition includes at least one from the groupconsisting of: an inorganic film, a metal film, and an organic film. 22.The method of claim 12, wherein the composite film deposition is formedusing at least one selected from the group consisting of: an atomiclayer deposition (ALD), an atomic layer epitaxy (ALE), a chemical vapordeposition (CVD), plasma enhanced chemical vapor deposition (PECVD), andremote plasma enhanced chemical vapor deposition (RPECVD).
 23. Themethod of claim 12, wherein the composite film deposition forms amulti-layer barrier film over at least a portion of an organic lightemitting device (OLED).
 24. The method of claim 12, further comprising:detecting, with a sensor, one or more surface features of a device,wherein the composite film deposition is formed on the one or moredetected surface features of the device. 25-44. (canceled)